3.3. Ideal Gas and Ideal-Gas State n Solution 3.2 (a The derivative (@P/@T)y is determined by application of Eq, (3.5) to the case for which Vis constant and dV = 0 paT—KdP=0 (const V) aP\ _p_ 1487x107 oP 24 bar-°C-} ( ) xo eax ioe PEC (®) If f and x are assumed constant in the 10°C temperature interval, then for con- stant volume Eq. (3.6) can be written: Ppa Py +b (ty — Ty) = L bar +24 bar-°C“! x 10°C = 241 bar (© Direct substation into Eq, (3.6 gives: In [2 = (1.487 x 108}(-20) ~ (62 x 10-6}(9) = 0.0303 i ¥29.9102 and V2=(0.9702\1.287)=1.249 ome 1 Then, AV= Vp ~ Vj = 1.249 ~ 1.287 = -0.038 em}. ‘The preceding example illustrates the fact that heating a liquid that completely fills a closed ‘vessel can cause a substantial rise in pressure. On the other hand, liquid volume decreases very slowly with rising pressure. Thus, the very high pressure generated by heating a subcooled liquid at constant volume can be relieved by a very small volume increase, or a very small leak in the constant volume container. 3.3. IDEAL GAS AND IDEAL-GAS STATE In the 19th century, scientists developed a rough experimental knowledge of the PVT behavior of gases at moderate conditions of temperature and pressure, leading to the equation PV = KT. wherein Vis molar volume and R is a universal constant, This equation adequately describes PYT behavior of gases for many practical purposes near ambient conditions of T and P. How- ‘ever, more precise measurements show that for pressures appreciably above, and temperatures appreciably below, ambient conditions, deviations become pronounced. On the other hand, deviations become ever smaller as pressure decreases and temperature increases. ‘The equation PV = RT'is now understood to define an ideal gas and to represent a model of behavior mote or less approximating the behavior of real gases. It is called the ideal gas Jaw, but is in fact valid only for pressures approaching zero and temperatures approaching.8 CHAPTER 3. Volumetric Properties of Pure Fluids infinity. Thus, itis @ Jaw only at limiting conditions. As these limits are approached, the mol- ‘ecules making up a gas become more and more widely separated, and the volume of the mol- ecules themselves becomes a smaller and smaller fraction of the total volume occupied by the gas. Furthermore, the forces of attraction between molecules become ever smaller because of the increasing distances between them. In the zero-pressure limit, molecules are separated by infinite distances. Their volumes become negligible compared with the total volume of the gas, and the intermolecular forces approach zero. The ideal gas concept extrapolates this behavior to all conditions of temperature and pressure. ‘The internal energy of a real gas depends on both pressure and femperature, Pressure dependence results from intermolecular forces. If such forces did not exist, no energy would be required to alter intermolecular distances, and no energy would be required to bring about pressure and Volume changes in a gas at constant temperature, Thus, in the absence of inter- ‘molecular forces, internal energy would depend on temperature only. These observations are the basis for the concept of a hypothetical state of matter designated the ideal-gas state, Its the state of a gas comprised of real molecules that have negligible molecular volume and no intermolecular forces at all temperatures and pressures. Although related to the ideal gas, it presents a different perspective. It is not the gas that is ideal, but the state, and this has practical advantages. Two equations are fundamental to this state, namely the “idcal-gas law” and an expression showing that internal energy depends on ‘temperature alone: + The equation of state: [Pv RT| Bn + Internal energy: G8) ‘The superscript ig denotes properties for the ideal-gas state. ‘The property relations for this state are very simple, and at appropriate conditions of T ‘and P they may serve as suitable approximations for direct application to the real-gas state. However, they have far greater importance as part of a general three-step procedure for calcu- lation of property changes for real gases that includes a major step in the ideal-gas state. The three steps are as follows: 1, Evaluate property changes for the mathematical transformation of an initial real-gas state into the ideal-gas state at the same T and P. 2, Caleulate property changes in the ideal-gas state for the Tand P changes of the process, 3. Evaluate property changes for the mathematical transformation of the ideal-gas state back to the real-gas state a the final T and P. This procedure calculates the primary property-value changes resulting from T and P changes by simple, but exact, equations for the ideal-gas state. The property-value changes for transitions between real and ideal-gas states are usually relatively minor corrections. These transition calculations are treated in Chapter 6, Here, we develop property-value calculations for the ideal-gas state.3.3. Ideal Gas and Ideal-Gas State 9 Property Relations for the Ideal-Gas State ‘The definition of heat capacity at constant volume, Ea, (2.15), leas forthe ideal-gas state to ‘he conclusion that C¥ isa funetion of temperature only ip. (av®) _ aviecry ct (wt) 20 oO G9) The defining equation for enthalpy, Eq. (2.10), applied to the ideal-gas state, leads to the ‘conclusion that [7 is also a function only of temperature: His = Us + PVE=U8 + RT= HED) G10) The heat capacity at constant pressure Cif, defined by Eq, (2.19), like Cf, is a function of temperature only ip (0H) _ at ct= ($F), WO < cen eu useful elation between C}! and Cf forthe ideal-gas state comes from diferentation of Fg (3.10) sig _dH®_ duit aor ark 12) This equation does not mean that Cif and Cff are themselves constant for the ideal-gas slate, ‘but only that they vary with temperature in such a way that their difference is equal to R. For any change in the ideal-gas state, Eqs. (3.9) and (3.11) lead to du*e=CHar G.13a) aves [gar 6.136) ane= Char @.14a) | ane = / Car G.14b) Because both U' and C¥ fr the idea-gas state are Functions of temperature only, AU'® for te ideal-gas state is always given by Eq, (3.130), regardless ofthe kind of process causing the change. This is illustrated in Fi. 3.5, which shows a graph of internal energy as a function of Vi at two different temperatures The dashed line connecting points a and b represents a constan-volume process for which the temperature inereases from T; to Ty and the internal energy changes by AU'® =U = U¥ This change in internal energy is given by Eq. (3.13b) as AU'* = / CfdT. The dashed lines connecting points @ and c and points a and d represent other processes not occurring at constant volume but which also lead from an inital temperature 7; toa final temperature Tp, The graph shows that the change in U fr these processes is the same as forthe constant-volume proces, and its therefore given by the same equation, namely, AU = [ C#dT. However, AU'® is not equal t @ for these processes, because Q depends not only on 7 and 7; bat also on the path of the process. An entirely analogous discussion applies tothe enthalpy #7 in the ideal-gas sate80 CHAPTER 3. Volumetric Properties of Pure Fluids Figure 3.5: Internal energy changes forthe ideal-gas state, Because U is independent (of VE, the plot of Ut vs. V¥ at constant femperature is a horizontal line. For diferent temperatures, Ut has different values, with a separate line foreach temperature. Two such lines are shown, one for temperature T, and ‘one for higher temperature Ts Process Calculations for the Ideal-Gas State Process calculations provide work and heat quantities. The work of a mechanically reversible closed-system process is given by Eq. (1.3), here written: awe pave a3) For the ideal-gas state in any closed-system process, the first law as given by Eq. (2.6) written for a unit mass or a mole, may be combined with Eq, (3.13a) to give: dQ+dW= Char Substitution for dW by Eq, (1.3) and solution for d@ yields an equation valid for the ideal-gas slate in any mechanically reversible closed-system process: dQ=Ciar+ Pave @.15) This equation contains the variables P, V*, and 7, only two of which are independent. Working equations for d@ and dW depend on which pair of these variables is selected as independent; ie., upon which variable is eliminated by Eq. (3.7). We consider two cases, climinating first P, and second, Vt, With P= RT/V'*, Eqs. (3.15) and (1.3) become: le av avi ag= charset 3.16) |aW=-RT G.I) Rode For View rip, ave = Rar 742), substituting for dV and for C= Cf —R wansforms Eqs. (3.15) and (1.3) intd @ P aQ=CilaT- RT G.18) | dW= RAT + RTS 3.19) ‘These equations apply to the ideal-gas state for various process calcula- tions. The assumptions implicit in their derivation are that the system is closed and the process is mechanically rever3.3. Ideal Gas and Ideal-Gas State 81 Isothermal Process By Eqs. (3.13b) and (3.146), AU = AH'€=0 (const) vat PL By Eqs. G16) and @.18), Q=RTIn = RTI i 2 vit By Eqs. (3.17) and G.19), W=RTIn y Bags. ( G19), vi a Because Q-=—W, a result that also follows from Eq, (2.3), we ean write in summary: vE Pi 2 Tin =RT In! (const 620) ve Py Isobaric Process By Eas. (3.136) and (3.19) with dP =0, vie = [cea and W=-R(T;—T)) By Eqs. (3.146) and 3.18), Q=ane I Char (const P) 20 Isochoric (Constant-V) Process With dV" = 0, W=0, and by Eqs. (3.136) and (3.16), o= au [car (const V*) 22 Adiabatic Process; Constant Heat Capacities ‘An adiabatic process is one for which there is no heat transfer between the system and its surroundings; ie., 42 = 0. Each of Eqs. (3.16) and (3.18) may therefore be set equal to ze. Integration with Ci and Cif constant then yields simple relations among the variables T, P, and V's, valid for mechanically reversible adiabatic compression or expansion in the ideal-gas state with constant heat capacities. For example, Eq, (3.16) becomes: aT Rave Tce ve82 CHAPTER 3. Volumetric Properties of Pure Fluids vnc t_ (vie Tye Integration with C¥ constant gives: Similarly, Eq, (3.18) leads to: const 23) | INT fonst (3.230) TWiey’=! = const (3.234) where Eq, (3.23c) results by combining Eqs. (3.238 and (3.23b) and where by definition,* e 3.24) Equations (3.23) apply for the ideal-gas state with constant heat capaci- ties and are restricted to mechanically reversible adiabatic expansion or compression. The first law for an adiabatic process in a closed system combined with Eq. (3.133) yields aw=au=Char For constant Ci, W=avie=c¥ar (3.25) Alternative forms of Eq, (3.25) result if Cf is eliminated in favor ofthe heat-capacity ratio y Ch_c+R_ | R aR pe FR Ry cee cece a rt and ‘Af and CE ae constant ys neces constant, The assumption f constant sequin tothe assuption that the heat capacies themselves ae constant. This isthe only way tht the ratio G/CM and the dfeence Gi-Ci = Ran both be constant. Except forthe monatomic gases, both Cy and C actualy increase with temperature bute sti less sensitive to temperature than the heat paces themscives4.3, Leal Gas and Ideal-Gas State 83 Because RT; = P, Vif and RT, = P2V¥, this expression may be writen: ary mT _ Paves nt 3.26) Equations (3.25) and (3.26) are general for adiabatic compression and expansion processes ina closed system, whether reversible ornot, because P, V, and T are state functions, independent of path. However, Tp and Vi are usually unknown, Elimination of Vie from Eq. (3.26) by Eq. (3.23c), valid only for mechanically reversible processes, leads to the ay ele] ‘The same result is obtained when the relation between P and V given by Eq, (3.23) is used for the integration, W=—/ Pat Pivit y-1 Equation (3.27) is valid only for the ideal-gas state, for constant heat capacities, and for adiabatic, mechanically reversible, closed-system processes. ‘When applied to real gases, Eqs. (3.23) through (3.27) often yield satisfactory approxi- ‘mations, provided the deviations from ideality are relatively small. For monatomic gases, y= 1.67; approximate values of y are 1.4 for diatomic gases and 1.3 for simple polyatomic gases such as CO, SO2, NH, and CH,, Irreversible Processes All equations developed in this section have been derived for mechanically reversible, closed-system processes for the ideal-gas state. However, the equations for property changes— dU", di, AU", and AH'*—are valid for the ideal-gas state regardless of the process. They apply equally to reversible and irreversible processes in both closed and open systems, because cchanges in properties depend only on initial and final states of the system. On the other hand, ‘an equation for Q or W, unless itis equal to a property change, is subject to the restrictions of its derivation ‘The work of an irreversible process is usually calculated by a two-step procedure. First, W is determined for a mechanically reversible process that accomplishes the same change of state as the actual irreversible process. Second, this result is multiplied or divided by an efficiency to give the actual work. If the process produces work, the absolute value for the reversible process is larger than the value for the actual irreversible process and must be multiplied by an efficiency. If the process requires work, the value for the reversible process is smaller than the value for the actual irreversible process and must be divided by an efficiency. Applications of the concepts and equations of this section are illustrated in the examples ‘that follow. In particular, the work of irreversible processes is treated in Ex. 3.5,84 CHAPTER 3. Volumetric Properties of Pure Fluids Example 3.3 Airis compressed from an intial state of 1 bar and 298.15 K to a fina state of 3 bar and 298,15 K by throe ifferent mechanically reversible processes ina closed system (0) Heating at constant volume followed oy cooling at constant pressure. (6) Isothermal compression, (©) Adiabatic compression followed by cooling at constant volume. ‘These processes are shown inthe figure, We assume at to be in ts ideal ga stat, and assume constant heat capacities, C= 20.785 and C= 29.100 Jmol! Calculate the work required, heet transfered, andthe changes In internal energy and enthalpy ofthe air for each process, Par vi 10% mt Solution 3.3 ‘Choose the system as 1 mol of air. The initial and final states of the air are identi cal with those of Ex. 2,7. The molar volumes given there are vit =002479 m? Vs = 0.008263 m’ Because Tis the same atthe beginning and end ofthe process, in all cases, Aus He =0 (a) The process here is exactly that of Ex. 2.7(b), for which: Q=~4958) and W=49585 (b) Equation (3.20) for isothermal compression applies. The appropriate value of Rhere (from Table A.2 of App. A) is R= 8.314 Jmol--K~! = -W= rin ®! ~ .314)298.15) In 4 = -273 1 rm 3 (©) The initial step of adiabatic compression takes the air to its final volume of (0.008263 m?. By Eq, (3.23), the temperature at this point is:3.3. Ideal Gas and Ideal-Gas State 85 vie 0.02479 \°" ren(tS) ~emio( QB)" For this step, @ = 0, and by Eq, (3.25), the work of compression is: W= CH ar=ciler — 7) = 20.785) (462.69 — 298.15) = 3420) For the constant-volume step, no work is done; the heat transfer is: 2 34205 vie 0.785 (298.15 — 462.69) (3-7) ‘Thus for process (c), 34203 4203 and Q Although the property changes AU! and AH are zero for each process, Q and Ware path-dependent, and here Q = -W. The figure shows each process on a PV" diagram. Because the work for each of these mechanically reversible processes is given by W= — [ Pd Vt, the work for each process is proportional tothe total area below the paths on the PV diagram from 1 to 2. The relative sizes ofthese areas correspond to the numerical values of W. Example 3.4 [A gas in its Ideal-gas state undergoes the following sequence of mechanically reversible processes in a closed system (0) From an initial state of 70°C and 1 bar, itis compressed adiabatically to 150°C. (6) Itis then cooled from 150 to 70°C at constant pressure, (c) Finally, it expands isothermally to its original state. Calculate W, 2, AU®, and AH® for each ofthe three processes and for the entire cycle Take C= 12.471 and C8 = 20.785 Jmol! K"! Solution 3.4 Take asa basis 1 mol of gas, (a) For adiabatic compression, Q = 0, and. Au't=W= Cf ar=(12.471)150—70) = 998 3 AM = CH AT = 20.785)(150 ~ 70) = 16633 Pressure P> i found from Eq, (3.23b) Ty"? 150-+273.15)?5 (?) v( 1.689 bar PPG 70+ 273.1586 CHAPTER 3. Volumetric Properties of Pure Fluids Toc ee As0°¢ 3 (© For this constant-pressure process, = AH'* = CHE AT = 20.785)(70 — 150) = ~1663 1 AT-= (12.471)(10 ~ 150) = 998 3 W= AU't — Q = -998 — (~1663) = 665 1 (6) For this isothermal process, AU" and AH'® ate zero; Eq. (3.20) yields: 1.689 T 4953 8.314)(343.15) In For the entire eyele, Q = 0- 1663 + 1495 = -168 7 198 + 665 — 1495 = 1687 198 - 998 +0. 1663 — 1663 +0 ‘The property changes AU' and AH both are zero for the entire cycle because the initial and final states are identical. Note also that Q = —W for the eycle. This follows from the first law with AU = 0. Example 3.5 ithe processes of Ex 3.4 are cated out imeversibly but so as to accomplish exactly the same changes of stafe—the same changes in PT. U9, and H—tnenaiflerent values of Gand Wresut Caleuate O and W each step is cared out witha work efferency of 80% Solution 3.5 Ifthe same changes of state as in Ex. 3.4 are carried out by irreversible processes, the property changes for the steps are identical with those of Ex. 3.4, However, the values of Q and W change,3.3. Ideal Gas and Ideal-Gas State 87 (a) For mechanically reversible, adiabatic compression, the work is Woy = 998 J If the process is 80% efficient compared with this, the actual work is larger, and 998/0.80 = 1248 J. This step cannot here be adiabatic. By the first law, Q=aut—w 198 — 1248 = 250 (&) The work required for the mechanically reversible cooling process is 665 J. For the imeversible process, W = 665/0.80 = 831 J. From Ex. 3.4(b), AU! = —998 J, and = AU!« — W=—998 —831 =-1829) (©) As work is done by the system in this step, the irreversible work in absolute value is less than the reversible work of —1495 J, and the actual work done is: W= (0.80)(~1495) = -1196 11963 Q=Aut—w=0+119 for the entire cycle, AU and AM are zero, with o= w 250 — 1829 + 1196 = 248 + 831 — 119% ‘A summary of these results and those for Ex. 3.4 is given in the following table; values are in joules. Mechanically reversible, Ex. 3.4 Irreversible, Ex. 3.5 Aue AH® og w ave aH® Ww @ 9981663 0 998 | 998 1663-250 1248 ()) 998-1663 1663665 | 998-1663 -1829 831 oO. 0 0 1495-1495 0 0 1196-1196 Cycle 0 0-168 168, 0 0-883 883 TThe cycle is one which requires work and produces an equal amount of heat. ‘The striking feature of the comparison shown in the table is that the total work required when the cycle consists of three irreversible steps is more than five times the total work required when the steps are mechanically reversible, even though each irreversible step is assumed to be 80% efficient. Example 3.6 Air flows at a steady rate through a horizontal pipe to # partly closed valve The pipe leaving the valve is enough larger than the entrance pipe that the kinetic-energy change of the airs it flows through the valve 's negligible, The valve and connecting pipes are wel insulated, The conditions of the alr upstream from the valve ore 20°C tnd 6 bar, and ine downstream pressures 3 bar Ifthe air is init ideal gas sate, what isthe temperature ofthe ir some distance downstream from the vaive?88 CHAPTER 3. Volumetric Properties of Pure Fluids Solution 3.6 Flow through a partly closed valve is known as a throttling process, The system is insulated, making Q negligible; moreover, the potental-energy and kinetic- energy changes are negligible, No shaft work is accomplished, and W, = 0. Hence, Eq, (2.31) reduces to AH'§=H!—H} =0, Because H'* is a function of temperature only, this requires that Ta = Ty, The result that A/V# = 0 is general for a throttling process, because the assumptions of nepigble heat transfer and potental- and kinetic- energy changes are usually valid, For a fluid in its ideal-gas state, no temperature change occurs, The throting process is inherently irreversible but this is immaterial 0 the calculation because Eq. (3.14b) is valid for the ideal-gas state whatever the process. Example 3.7 If in Ex. 3.6 the flow rate of air is 1 mol-s~! and if both upstream and downstream pipes have an inner diameter of § em, whatis the kinetic-energy change of the air anc what is its temperature change? For air, Ci-= 29.100 Jmol"! and the molar mass is, Mt = 29 g-mol"’, Solution 3.7 By Eq, (2.236), where fpr. (2 2)? 3 m2 py = (Z) 6x10 )2 = 1.964 x 10 A The appropriate value here of the gas constant for calculation of the upstream molar volume is R = 83.14 x 10 barm?.molK-?, ‘Then RT _ (83.14 10-9)293.15K) wR, bar = 4.062 x 10°? m?-mol! Then, (mols (4.062 x 1073 m?.moI™! 1.964% 105m? 2.069 ms! If the downstream temperature is litle changed from the upstream temperature, then to a good approximation: and up =2uy = 4.138 ms~ vs The toting of real gases may result in a relatively smal temperate inzease or decrease, known a the Joule! “Thomson effet. Amore detied discussion is found in Chapter 7.3.4. Virial Equations of State 89 ‘The rate of change in kinetic energy is therefore: 1 1 mA( su?) =A. sue a(3e*) =i a() (4.1382 — 2,0692)m2.s = (129% 10-9 kg,s-1} EEE 7009 ms 2 = 0.186 kg-m™s- = 0.186 Js! In the absence of heat transfer and work, the energy balance, Eq. (2.30), becomes: (neha anes nd (he i) = ma(5u 1 1 euancparsna(5u) aac aT + mal 3) =0 ) = -0.86 0 Then 1 ven1098r=-a( and AT=~0,0064K Clearly, the assumption of negligible temperature change across the valve is jus- tified. Even for an upstream pressure of 10 bar and a downstream pressure of 1 bar and for the same flow rate, the temperature change is only ~0.076 K. We conclude ‘that, except for very unusual conditions, AH = 0 is a satisfactory energy balance. 3.4 VIRIAL EQUATIONS OF STATE Volumetric data for fluids are useful for many purposes, from the metering of fluids to the sizing of tanks, Data for Vas a function of T and P can of course be given as tables, However, expression of the functional relation /(P, V, T) = 0 by equations is much more compact and convenient. The virial equations of state for gases are uniquely suited to this purpose. Tsotherms for gases and vapors, lying to the right of the saturated-vapor curve CD in Fig. 3.2(), are relatively simple curves for which V decreases as P increases. Here, the product PV for a given T varies much more slowly than either of its members, and hence is more easily represented analytically as a function of P. This suggests expressing PV for an isotherm by a power series in P: PV=a+ bP +eP?+ If we define, b= ab, c= aC’ etc, then, PV=a(1 + BP+CP4DP +...) 3.28) where BY, C’ etc, are constants for a given temperature and a given substance,